CN113668091B - High-strength high-elongation heterocyclic aromatic polyamide fiber and preparation process thereof - Google Patents
High-strength high-elongation heterocyclic aromatic polyamide fiber and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a high-strength high-elongation heterocyclic aromatic polyamide fiber and a preparation process thereof, belonging to the field of special organic fibers. According to the invention, the molecular structure of the heterocyclic aramid fiber is introduced with the modified monomers such as chlorine-containing p-phenylenediamine, 2, 5-diaminobenzonitrile, m-phenylenediamine, 4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether and the like, so that the aims of greatly improving the elongation and having better composite performance are achieved while the high tensile breaking strength of the heterocyclic aramid fiber is maintained. The spinning solution obtained by polymerization is subjected to deaeration, filtration, plastic stretching, washing, drying, oiling and heat treatment, and finally wound to obtain the finished fiber, the tensile breaking strength of the high-strength and high-elongation heterocyclic aromatic polyamide fiber is 28.0-35.0 cN/dtex, the elongation is 4.5-10.0%, and the fiber has wide application prospect in the fields of national defense and military industry, particularly the bulletproof field and the special rubber reinforcement field.
Description
Technical Field
The invention relates to a preparation method of heterocyclic aromatic polyamide fiber, in particular to heterocyclic aromatic polyamide fiber with high strength and high elongation and a preparation process thereof, belonging to the field of preparation of special organic fiber.
Background
The heterocyclic aromatic polyamide fiber is also called heterocyclic aramid fiber or aramid fiber III and is prepared by introducing heterocyclic aromatic diamine on the basis of para-aramid fiber (aramid fiber II). The introduction of the heterocyclic diamine destroys the regularity of the para-aramid structure and slows down the crystallization speed of the para-aramid, so that the heterocyclic diamine is beneficial to improving the stretching ratio and the orientation degree of the fiber in the spinning process, and the heterocyclic aramid has more excellent strength and modulus. However, similar to other high-performance fibers, the elongation at break of the heterocyclic aramid fiber is low, and table 1 shows that the mechanical property indexes of several high-performance organic fibers commercialized at present are only about 2.0% -4.5% in elongation. The reason is that high-performance fibers must be highly drawn during the preparation process to increase the crystallinity and orientation of the fibers to obtain excellent properties of high strength and high modulus, but at the same time, the elongation at break is reduced.
TABLE 1 commercial major high Performance organic fiber varieties and their Properties and compositions
On the basis of keeping high strength, the elongation at break of the heterocyclic aramid fiber is improved, and the application performance of the heterocyclic aramid fiber in some special fields is improved. As in the field of ballistic protection, U.S. researchers proposed ballistic performance coefficients (U) with fibers in the 90's of the 20 th century * ） 1/3 To evaluate the ballistic performance of the fibers,
where σ is tensile breaking strength, ε is elongation at break, ρ is fiber density, and E is Young's modulus. From this empirical formula, the ballistic performance of a fiber is proportional to its strength and elongation. Kevlar KM2 fiber with higher strength and elongation is prepared by DuPont on the basis of Kevlar 29, the bulletproof efficiency coefficient is 697m/s, and the Kevlar series fiber is the first fiber; in the field of rubber reinforcement, the fatigue resistance of the aramid fiber can be obviously improved by improving the elongation at break of the aramid fiber. DuPont discloses para-aramid fibers particularly suitable for tire cords in patents US4859393, US4902774 and US5173236, wherein only 0.05-0.2 g/d of tensile tension is applied to the fibers in the spinning process, the elongation of Kevlar fibers is successfully improved from 3.0-3.5% to 4.5-5.6% by reducing the tensile multiple of the fibers, and research results show that the fatigue resistance of the fibers is remarkably higher than that of common Kevlar fibers, and the fibers are particularly suitable for the field of rubber reinforcement. But because the stretching multiple is low, the strength of the para-aramid prepared by the method is only 18-24 g/d (about 2.25-3.00 GPa).
At present, researches on heterocyclic aramid fibers are mostly focused on further improving the mechanical strength and the composite performance of the heterocyclic aramid fibers, for example, in patent CN104357939A, a chlorine-containing monomer is adopted to modify aramid fiber III, and the prepared fiber has good composite performance, the strength can reach 24-32 cN/dtex, but the elongation is only 2.3-4.0%. CN107675283A uses 2, 5-diaminobenzonitrile to modify aramid III fiber, the prepared fiber has good resin composite property, the strength of the dipped yarn can reach 3.5-5.5 GPa, but the elongation at break is only 2.5% -4.5%. On the basis of maintaining excellent mechanical strength of the heterocyclic aramid fiber, reports of greatly improving the elongation are few.
Disclosure of Invention
The invention aims to provide a heterocyclic aromatic polyamide fiber with high strength and high elongation against the defect of low elongation of the conventional high-strength heterocyclic aramid fiber. The invention starts from the design of molecular structure, and achieves the purpose of greatly improving the elongation and having better composite performance while maintaining the high tensile breaking strength of the heterocyclic aramid fiber by introducing modified monomers such as chlorine-containing p-phenylenediamine, 2, 5-diaminobenzonitrile, m-phenylenediamine, 4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether and the like into the molecular structure of the heterocyclic aramid fiber.
Another object of the present invention is to provide a method for preparing a high-strength high-elongation aromatic heterocyclic polyamide fiber
And (5) processing. The invention uses 2- (4-aminophenyl) -5-aminobenzimidazole, p-phenylenediamine, 4' -diaminodiphenyl ether, chlorine-containing p-phenylenediamine and other diamine monomers as raw materials, and the diamine monomers and terephthaloyl chloride (TPC) are polymerized in an organic solvent to obtain spinning solution, and then the spinning solution is spun to obtain the high-strength high-elongation heterocyclic aromatic polyamide fiber. The process method has the advantages of simple and feasible industrial implementation, and the prepared heterocyclic aramid fiber not only has excellent mechanical strength, but also has extremely high elongation at break and composite performance, so that the heterocyclic aramid fiber has wide application prospect in the field of national defense and military industry, particularly the field of bulletproof and the field of special rubber reinforcement.
The purpose of the invention is realized by the following technical scheme: a high-strength high-elongation heterocyclic aromatic polyamide fiber, the molecular composition structure of which is formed by randomly connecting 4 kinds of repeating units with the following structural formula,
wherein the content of the first and second substances,
ar in repeating unit (III) 1 Is composed of
At least one of;
ar in the repeating unit (IV) 2 Is composed of
At least one of;
the molar percentage content of each repeating unit in the molecular composition structure is as follows:
the content of the repeating unit (I) is 40-90%;
the repeating unit (II) is 0 to 30 percent;
the content of the repeating unit (III) is 5-30%;
the content of the repeating unit (IV) is 5 to 30 percent.
In the invention, the repeating unit (I) is 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI), and the repeating unit (II) is p-phenylenediamine (PPDA), and the two repeating units are main composition structures of the heterocyclic aramid fiber. The introduction of DAPBI of the repeating unit (I) destroys the regularity of the molecular structure of para-aramid (PPDA) of the repeating unit (II) and slows down the crystallization speed, so that the stretching ratio and the orientation degree of the fiber are improved in the spinning process, and the heterocyclic aramid has more excellent strength and modulus than the para-aramid. The content of the repeating unit (II) is not essential for the heterocyclic aramid of the present invention and may be 0, however, it is preferable to add part of PPDA for copolymerization from the viewpoint of cost reduction, but the content of the repeating unit (II) is not more than 30% by mole, otherwise the mechanical properties of the fiber are affected.
In the invention, the repeating unit (III) is m-phenylenediamine (MPDA), 4 '-diaminodiphenyl ether (DADPE) or 3,4' -diaminodiphenyl ether (MADPE) modified monomer, belongs to a semi-rigid or non-extended chain structural unit, has a certain bond angle, and is firstly extended along the direction of an external force when the fiber is stretched by the external force to generate larger deformation, thereby greatly improving the elongation at break of the fiber. And the elongation of the fiber increases with the increase of the content, but the semi-rigid or non-extended chain structure simultaneously causes the reduction of the strength of the fiber, so that the molar content is not higher than 30% in terms of the comprehensive strength and elongation.
In the invention, the repeating unit (IV) is chlorine-containing p-phenylenediamine (Cl-PPDA) or 2, 5-diaminobenzonitrile (CN-PPDA), is a modified monomer with a rigid structure containing polar side groups, slows down the crystallization speed, increases the interaction force among molecules and is beneficial to realizing high-power stretching; and the strength of the dipped yarn is greatly improved due to the existence of the polar side group. When the fiber is used in the fields of elasticity resistance and rubber compounding, the bonding force with a resin or rubber matrix is greatly improved, and the reduction of the mechanical property of the fiber, particularly the strength after gum dipping, caused by the introduction of a repeating unit (III) is avoided.
A preparation process of high-strength high-elongation heterocyclic aromatic polyamide fiber comprises the following steps:
A. preparation of polymerization stock solution: dissolving diamine monomers in proportion into an organic solvent containing solubilizing salts, then adding terephthaloyl chloride, and stirring and reacting under the protection of nitrogen to obtain a polymer solution;
the solid content of the polymer solution is 3-10%, and the dynamic viscosity is 3-80 ten thousand centipoise at room temperature;
among them, the solid content is preferably 4 to 6% and the kinetic viscosity is preferably 5 to 20 ten thousand centipoise.
It is well known that the dynamic viscosity of a polymer solution affects the spinnability of the solution and the final properties of fibers, and the dynamic viscosity of a polymer is mainly affected by various factors such as the molecular weight, temperature, solid content and molecular structure of the polymer. The solid content of the polymer is too high, the molecular weight of the polymer needs to be reduced under the condition of maintaining the dynamic viscosity with better spinnability, and the improvement of the mechanical property of the fiber is not facilitated; and when the solid content is too low, the primary fiber is solidified, the defects of more pores and the like are generated inside, the mechanical strength of the fiber is not improved, and the production efficiency is reduced. Therefore, the solid content of the polymer solution is controlled to be 3-10%, and the dynamic viscosity is 3-80 ten thousand centipoise at room temperature.
B. Spinning: transferring the polymer solution obtained in the step A into a defoaming kettle, defoaming, filtering, extruding the polymer solution through a spinneret orifice, coagulating and forming the polymer solution in a coagulating bath to obtain nascent fibers, plastically stretching, washing, drying and oiling the nascent fibers, then performing a heat treatment process, and finally winding to obtain finished fibers;
the tensile breaking strength of the finished fiber is 28.0-35.0 cN/dtex, and the elongation is 4.5-10.0%.
In step A, the diamine monomer comprises 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) corresponding to the repeating unit (I), p-phenylenediamine (PPDA) corresponding to the repeating unit (II), at least one of m-phenylenediamine (MPDA), 4 '-diaminodiphenyl ether (DADPE), 3,4' -diaminodiphenyl ether (MADPE) corresponding to the repeating unit (III), and at least one of chlorine-containing p-phenylenediamine (Cl-PPDA), 2, 5-diaminobenzonitrile (CN-PPDA) corresponding to the repeating unit (IV).
Further, the chlorine-containing p-phenylenediamine (Cl-PPDA) comprises 2-chlorine-containing p-phenylenediamine, 2, 5-dichloro-containing p-phenylenediamine and 2, 6-dichloro-containing p-phenylenediamine.
In the step A, the dissolution-assisting salt is LiCl or CaCl 2 But preferably a single component salt from the viewpoint of recovery of the salt and waste liquid treatment;
the solid content of the dissolution assisting salt in the organic solvent is 2.0-7.5%;
the organic solvent is one of N, N-dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP).
The coagulating bath uses 30-65% by mass of an aqueous solution of N, N-dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP), and the temperature of the coagulating bath is 0-40 ℃.
The addition of a certain proportion of solvent (DMAc or NMP) into the coagulant water helps to slow down the coagulation speed, reduce the defects of the sheath-core structure and the nascent fiber and improve the mechanical properties of the fiber. However, when the concentration of the coagulation bath is too high, the fibers are insufficiently coagulated, and the concentration of the spinning coagulation bath is preferably 30 to 65 percent; in order to facilitate the recovery and utilization of the solvent, it is preferable that the type of the solvent to be added to the coagulation bath is the same as the type of the solvent to be used for the polymerization.
In the step B, the plastic stretching is carried out in an aqueous solution of N, N-dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP) with the mass fraction of 10-25% at the temperature of 20-70 ℃.
In the step B, the water used in the water washing procedure is hot water with the temperature of 80-95 ℃, and the water washing mode adopts an inclined roller method of upper spraying and lower immersing.
In the step B, the oiling procedure is to continuously pass the tows through an aqueous emulsion containing an oiling agent.
In the step B, the drying process adopts a contact roller for drying, and the drying temperature is 120-200 ℃, preferably 140-160 ℃.
In the step B, the heat treatment process is channel type non-contact heat treatment or roller type contact heat treatment, and the heat treatment is carried out for 0.5 to 5min at 320 to 450 ℃ in the atmosphere of air or nitrogen; preferably, the heat treatment is carried out for 3 to 4min at 350 to 380 ℃ in a nitrogen environment.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention starts from the design of molecular structure, modified monomers such as chlorine-containing p-phenylenediamine, 2, 5-diaminobenzonitrile, m-phenylenediamine, 4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether and the like are introduced into the molecular structure of the heterocyclic aramid fiber, the performance structure of each monomer is fully utilized, and the heterocyclic aramid fiber is ensured to maintain the high tensile breaking strength of the heterocyclic aramid fiber and achieve the great improvement of the elongation and better composite performance by slowing down the crystallization speed, increasing the interaction force among molecules, increasing the deformation, improving the dipping silk strength and the like.
2. The introduction of modified monomers such as chlorine-containing p-phenylenediamine and 2, 5-diaminobenzonitrile further reduces the regularity of the heterocyclic aramid structure, slows down the crystallization speed of the para-aramid and is beneficial to realizing high-power stretching to obtain higher strength; meanwhile, modified monomers such as m-phenylenediamine (MPDA), 4 '-diaminodiphenyl ether (DADPE), 3,4' -diaminodiphenyl ether (MADPE) and the like belong to a semi-rigid non-extended chain structure, a certain bond angle exists in a molecular main chain, and the non-extended chain structure can be firstly extended along the direction of external force action when being stretched by external force, so that the breaking elongation of the fiber is greatly improved. The tensile breaking strength of the heterocyclic aromatic polyamide fiber is 28.0-35.0 cN/dtex, the elongation is 4.5-10.0%, and the fiber has the obvious advantages of high strength and high elongation.
3. The invention uses 2- (4-aminophenyl) -5-aminobenzimidazole, p-phenylenediamine, 4' -diaminodiphenyl ether, chlorine-containing p-phenylenediamine and other diamine monomers as raw materials, and the diamine monomers and terephthaloyl chloride (TPC) are polymerized in an organic solvent to obtain spinning solution, and then the spinning solution is spun to obtain the high-strength high-elongation heterocyclic aromatic polyamide fiber. The method has the advantages of simple and feasible industrial implementation, and the prepared heterocyclic aromatic polyamide fiber can be widely applied to the fields of aviation, aerospace, weaponry and the like. The rubber composite material has ultrahigh strength and high elongation, so that the fatigue resistance of the rubber composite material can be greatly improved, and the interfacial composite performance of fiber and the rubber material is improved due to the introduction of monomers containing polar side groups such as chlorine-containing p-phenylenediamine, 2, 5-diaminobenzonitrile and the like, so that the rubber composite material is particularly suitable for the field of special rubber reinforcement, such as tires of military fighters and the like. In addition, the invention has high strength and high elongation, greatly improves the bulletproof efficacy, and is particularly suitable for the fields of armor bulletproof, individual protection and the like.
Drawings
FIG. 1 is a graph comparing the strength (% cN/dtex) versus% elongation curves for the final heterocyclic aromatic polyamide fiber products of examples 2, 9 and 11 according to the invention and comparative examples
In the figure: 1-comparative example; 2-example 9; 3-example 11; 4-example 2.
Detailed Description
In order to better explain the present invention, the present invention is described in detail with reference to the following examples, which should be construed as merely illustrative and not limitative of the remainder of the disclosure, and the modifications and variations that would be apparent to those skilled in the art are intended to be included within the scope of the present invention.
Example 1
A high-strength high-elongation heterocyclic aromatic polyamide fiber, the molecular composition structure of which is formed by randomly connecting 4 kinds of repeating units with the following structural formula,
wherein, the first and the second end of the pipe are connected with each other,
ar in the repeating unit (III) 1 Is composed of
Ar in the repeating unit (IV) 2 Is composed of
；
The molar percentage content of each repeating unit in the molecular composition structure is as follows:
the repeating unit (I) is 40 percent of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI);
the content of the repeating unit (II) p-phenylenediamine (PPDA) is 30 percent;
the content of the repeating unit (III) m-phenylenediamine (MPDA) is 20 percent;
the content of the repeating unit (IV) 2-chloro-p-phenylenediamine is 10 percent;
through tests, the tensile breaking strength of the high-strength high-elongation heterocyclic aromatic polyamide fiber is 25.4cN/dtex, the elongation is 5.0%, the modulus is 666cN/dtex, and the strength of the dipped yarn is 5020MPa.
Example 2
A high-strength high-elongation heterocyclic aromatic polyamide fiber, the molecular composition structure of which is formed by randomly connecting 4 kinds of repeating units with the following structural formula,
wherein the content of the first and second substances,
ar in repeating unit (III) 1 Is composed of
Ar in the repeating unit (IV) 2 Is composed of
；
The mol percentage content of each repeating unit in the molecular composition structure is as follows:
the repeating unit (I) is 65% of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI);
15% of p-phenylenediamine (PPDA) in the repeating unit (II);
the repeating unit (III) 4,4' -diaminodiphenyl ether (DADPE) was 15%;
the repeating unit (IV) 2, 5-diaminobenzonitrile (CN-PPDA) is 5%;
the high-strength high-elongation heterocyclic aromatic polyamide fiber has the tensile breaking strength of 30.6cN/dtex, the elongation of 5.7 percent, the modulus of 509cN/dtex and the strength of the dipped yarn of 5297MPa.
Example 3
A high-strength high-elongation heterocyclic aromatic polyamide fiber, the molecular composition structure of which is formed by randomly connecting 3 kinds of repeating units with the following structural formula,
wherein the content of the first and second substances,
ar in repeating unit (III) 1 Is composed of
Ar in the repeating unit (IV) 2 Is composed of
；
The molar percentage content of each repeating unit in the molecular composition structure is as follows:
the repeating unit (I) is 90% of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI);
the repeating unit (III) 3,4' -diaminodiphenyl ether (MADPE) is 5%;
the content of the repeating unit (IV) 2, 5-dichloro-p-phenylenediamine is 5 percent;
the high-strength high-elongation heterocyclic aromatic polyamide fiber has the tensile breaking strength of 33.4cN/dtex, the elongation of 4.7 percent, the modulus of 827cN/dtex and the strength of the dipped yarn of 5411MPa.
Example 4
A high-strength high-elongation heterocyclic aromatic polyamide fiber, the molecular composition structure of which is formed by randomly connecting 4 kinds of repeating units with the following structural formula,
wherein the content of the first and second substances,
ar in the repeating unit (III) 1 Is composed of
；
Ar in the repeating unit (IV) 2 Is composed of
；
The molar percentage content of each repeating unit in the molecular composition structure is as follows:
the content of the repeating unit (I), namely 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI), is 45 percent;
the content of the repeating unit (II) p-phenylenediamine (PPDA) is 5 percent;
the total amount of m-phenylenediamine (MPDA) and 3,4' -diaminodiphenyl ether (MADPE), which are repeating units (III), is 30% by weight, and the two are combined in an arbitrary ratio;
the content of the repeating unit (IV) 2, 6-dichloro-p-phenylenediamine is 20 percent;
the high-strength high-elongation heterocyclic aromatic polyamide fiber has the tensile breaking strength of 26.8cN/dtex, the elongation of 6.7 percent, the modulus of 547cN/dtex and the strength of the dipped yarn of 5223MPa.
Example 5
A high-strength high-elongation heterocyclic aromatic polyamide fiber, the molecular composition structure of which is formed by randomly connecting 4 kinds of repeating units of the following structural formula,
wherein, the first and the second end of the pipe are connected with each other,
ar in the repeating unit (III) 1 Is composed of
；
Ar in the repeating unit (IV) 2 Is composed of
；
The mol percentage content of each repeating unit in the molecular composition structure is as follows:
the repeating unit (I) is 40 percent of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI);
25% of p-phenylenediamine (PPDA) as the repeating unit (II);
the repeating unit (III) 4,4' -diaminodiphenyl ether (DADPE) is 5%;
the total amount of the repeating unit (IV) 2, 5-diaminobenzonitrile (CN-PPDA), 2-chloro-p-phenylenediamine and 2, 5-dichloro-p-phenylenediamine is 30 percent, and the three are combined according to any ratio;
the high-strength high-elongation heterocyclic aromatic polyamide fiber has the tensile breaking strength of 25.9cN/dtex, the elongation of 4.4 percent, the modulus of 692cN/dtex and the strength of 5158MPa of dipped yarn.
Example 6
A high-strength high-elongation heterocyclic aromatic polyamide fiber is prepared by the following steps:
A. preparation of polymerization stock solution: 3 diamine monomers of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) (114.3053 g), 4' -diaminodiphenyl ether (DADPE) (5.6700 g) and 2-chloro-p-phenylenediamine (4.0353 g) in a molar ratio of 9.0.5 were dissolved in 3759g of an N, N-dimethylacetamide (DMAc) solution containing 2.0% lithium chloride, and then terephthaloyl chloride (TPC) (114.6192 g) was added in an amount of 99.7% based on the total moles of diamines, and the reaction was stirred for 1h under nitrogen protection to give a polymer solution with a solid content of 5% and a kinematic viscosity of 18.5 million centipoise at room temperature.
B. Spinning: and transferring the polymer solution into a deaeration kettle for deaeration, filtering the polymer solution after deaeration, extruding the polymer solution into a DMAc (dimethyl formamide) aqueous solution with the temperature of 40 ℃ and the mass fraction of 65 percent through a spinneret orifice for solidification and forming to obtain nascent fibers, plastically stretching the nascent fibers in the DMAc aqueous solution with the temperature of 30 ℃ and the mass fraction of 15 percent, then performing water washing, and washing with hot water at the temperature of 80 ℃ to remove residual solvent. Then drying and oiling at 120 ℃, treating for 3min at 380 ℃ in a nitrogen environment, and winding to obtain the finished fiber, wherein the fiber properties are shown in Table 2.
Example 7
A high-strength high-elongation heterocyclic aromatic polyamide fiber is prepared by the following steps:
A. preparation of polymerization stock solution: 3 diamine monomers of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) (71.8081 g), 4' -diaminodiphenyl ether (DADPE) (18.3200 g) and 2, 5-dichloro-p-phenylenediamine (8.1080 g) in a molar ratio of 7.
B. Spinning: and transferring the polymer solution into a defoaming kettle for defoaming, filtering, extruding the polymer solution through a spinneret orifice, coagulating and forming the polymer solution into a DMAc (dimethyl formamide) aqueous solution with the temperature of 10 ℃ and the mass fraction of 50% to obtain nascent fibers, performing 100% plastic stretching on the nascent fibers in the DMAc aqueous solution with the temperature of 20 ℃ and the mass fraction of 10%, then performing a water washing process, and washing with hot water at 85 ℃ to remove residual solvent. Then drying and oiling at 150 ℃, processing at 450 ℃ for 0.5min under the nitrogen environment, and winding to obtain the finished fiber, wherein the fiber properties are shown in Table 2.
Example 8
A high-strength high-elongation heterocyclic aromatic polyamide fiber is prepared by the following steps:
A. preparation of polymerization stock solution: 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) (46.5115 g), 4' -diaminodiphenyl ether (DADPE) (20.7600 g) and 2, 5-diaminobenzonitrile (4.6070 g) 3 diamine monomers in a molar ratio of 6.
B. Spinning: and transferring the polymer solution into a defoaming kettle for defoaming, filtering, extruding the polymer solution through a spinneret orifice into a 50 mass percent NMP (N-methyl pyrrolidone) aqueous solution at the temperature of 20 ℃ for solidification and forming to obtain nascent fibers, performing 70 percent plastic stretching on the nascent fibers in the 25 mass percent NMP aqueous solution at the temperature of 70 ℃, then performing water washing, and washing with hot water at the temperature of 85 ℃ to remove residual solvent. Then drying and oiling at 200 ℃, treating for 3min at 380 ℃ in a nitrogen environment, and winding to obtain the finished fiber, wherein the fiber properties are shown in Table 2.
Example 9
A high-strength high-elongation heterocyclic aromatic polyamide fiber is prepared by the following steps:
A. preparation of polymerization stock solution: 4 diamine monomers of 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) (74.3232 g), p-phenylenediamine (PPDA) (5.1192 g), 4' -diaminodiphenyl ether (DADPE) (9.4714 g) and 2-chloro-p-phenylenediamine (6.7445 g) in a molar ratio of 1.
B. Spinning: and transferring the polymer solution into a deaeration kettle for deaeration, filtering the polymer solution after deaeration, extruding the polymer solution into a DMAc (dimethyl formamide) aqueous solution with the temperature of 10 ℃ and the mass fraction of 50 percent through a spinneret orifice for solidification and forming to obtain nascent fibers, plastically stretching the nascent fibers in the DMAc aqueous solution with the temperature of 30 ℃ and the mass fraction of 20 percent, then performing water washing, and washing with hot water at the temperature of 85 ℃ to remove residual solvent. Then drying and oiling at 140 ℃, processing for 4min at 350 ℃ in a nitrogen environment, and winding to obtain the finished fiber, wherein the fiber properties are shown in Table 2.
Example 10
A high-strength high-elongation heterocyclic aromatic polyamide fiber is prepared by the following steps:
A. preparation of polymerization stock solution: 3 diamine monomers, 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) (76.3616 g), m-phenylenediamine (10.5192 g) and 2, 5-dichloro-p-phenylenediamine (8.6110 g), in a molar ratio of 7.
B. Spinning: and transferring the polymer solution into a deaeration kettle for deaeration, filtering the polymer solution after deaeration, extruding the polymer solution into a DMAc (dimethyl formamide) aqueous solution with the temperature of 0 ℃ and the mass fraction of 30 percent through a spinneret orifice for solidification and forming to obtain nascent fibers, plastically stretching the nascent fibers in the DMAc aqueous solution with the temperature of 30 ℃ and the mass fraction of 20 percent, then performing water washing, and washing with hot water at the temperature of 90 ℃ to remove residual solvent. Then drying and oiling at 150 ℃, treating for 3min at 380 ℃ in a nitrogen environment, and winding to obtain the finished fiber, wherein the fiber properties are shown in Table 2.
Example 11
A high-strength high-elongation heterocyclic aromatic polyamide fiber is prepared by the following steps:
A. preparation of polymerization stock solution: 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) (112.2688 g) and 4,4' -diaminodiphenyl ether (DADPE) (14.3200 g) in a molar ratio of 7.
B. Spinning: and transferring the polymer solution into a deaeration kettle for deaeration, filtering the polymer solution after deaeration, extruding the polymer solution into a DMAc (dimethyl formamide) aqueous solution with the temperature of 10 ℃ and the mass fraction of 40% through a spinneret orifice for solidification and forming to obtain nascent fibers, plastically stretching the nascent fibers in the DMAc aqueous solution with the temperature of 50 ℃ and the mass fraction of 25% through 120% and then entering a water washing process, and washing the nascent fibers with hot water at the temperature of 95 ℃ to remove residual solvent. Then drying and oiling at 120 ℃, processing for 3.5min at 360 ℃ in a nitrogen environment, and winding to obtain the finished fiber, wherein the fiber properties are shown in Table 2.
Example 12
A high-strength high-elongation heterocyclic aromatic polyamide fiber is prepared by the following steps:
A. preparation of polymerization stock solution: 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) (75.2640 g), 4' -diaminodiphenyl ether (DADPE) (9.6000 g) and 2, 5-diaminobenzonitrile (CN-PPDA) (12.7680) 3 diamine monomers in a molar ratio of 7.
B. Spinning: and transferring the polymer solution into a defoaming kettle for defoaming, filtering, extruding the polymer solution through a spinneret orifice, coagulating and forming in a DMAc (dimethyl formamide) aqueous solution with the temperature of 10 ℃ and the mass fraction of 50% to obtain nascent fibers, performing plastic stretching on the nascent fibers in a DMAc aqueous solution with the temperature of 30 ℃ and the mass fraction of 20% by 140%, then performing water washing, and washing with hot water at the temperature of 90 ℃ to remove residual solvent. Then drying and oiling at 180 ℃, processing for 2min at 400 ℃ in a nitrogen environment, and winding to obtain the finished fiber, wherein the fiber properties are shown in table 2.
Example 13
A high-strength high-elongation heterocyclic aromatic polyamide fiber is prepared by the following steps:
A. preparation of polymerization stock solution: DAPBI (143.2480 g), p-phenylenediamine (PPDA) (13.8132 g), MADPE (25.5800 g) and 2, 5-diaminobenzonitrile (CN-PPDA) (51.0321 g) 4 diamine monomers in a molar ratio of 5.
B. Spinning: and transferring the polymer solution into a defoaming kettle for defoaming, filtering, extruding the polymer solution through a spinneret orifice, coagulating and forming in a 50% DMAc aqueous solution at the temperature of 10 ℃, performing plastic stretching on 160% DMAc aqueous solution at the temperature of 30 ℃ and the mass fraction of 20% nascent fiber, washing in water, and washing with hot water at the temperature of 85 ℃ to remove residual solvent. Then drying and oiling at 160 ℃, processing for 1.5min at 420 ℃ in a nitrogen environment, and winding to obtain the finished fiber, wherein the fiber properties are shown in table 2.
Example 14
A high-strength high-elongation heterocyclic aromatic polyamide fiber is prepared by the following steps:
A. preparation of polymerization stock solution: DAPBI (91.2128 g), paraphenylene diamine (PPDA) (21.9888 g), DADPE (20.3600 g) and 2, 6-dichloro-paraphenylene diamine (54.0558 g) 4 diamine monomers in a molar ratio of 4.
B. Spinning: and transferring the polymer solution into a defoaming kettle for defoaming, filtering, extruding the polymer solution through a spinneret orifice, coagulating and forming in a DMAc (dimethyl formamide) aqueous solution with the temperature of 10 ℃ and the mass fraction of 50% to obtain nascent fibers, carrying out plastic stretching on the nascent fibers in a DMAc aqueous solution with the temperature of 30 ℃ and the mass fraction of 20%, then carrying out water washing, and washing with hot water at the temperature of 85 ℃ to remove residual solvent. Then drying and oiling at 140 ℃, treating for 3min at 380 ℃ in an air environment, and winding to obtain the finished fiber, wherein the fiber properties are shown in Table 2.
Comparative example
A heterocyclic aromatic polyamide fiber is prepared by the following steps:
A. preparation of polymerization stock solution: 2- (4-aminophenyl) -5-aminobenzimidazole (DAPBI) (75.7499 g) and p-phenylenediamine (PPDA) (18.2337 g) in a molar ratio of 6.67 to 3.33 were dissolved in 3803g of a DMAc solution containing 3.5% lithium chloride, TPC (102.5924 g) was added in an amount of 99.8% based on the total moles of diamine, and the reaction was stirred under nitrogen for 1 hour to give a polymer solution having a solid content of 4% and a kinetic viscosity of 6.5 ten thousand cps at room temperature.
B. Spinning: and transferring the polymer solution into a defoaming kettle for defoaming, filtering, extruding the polymer solution through a spinneret orifice, coagulating and forming the polymer solution into a DMAc (dimethyl formamide) aqueous solution with the temperature of 20 ℃ and the mass fraction of 50% to obtain nascent fibers, performing 150% plastic stretching on the nascent fibers in the DMAc aqueous solution with the temperature of 20 ℃ and the mass fraction of 15%, then performing a water washing process, and washing with hot water at the temperature of 90 ℃ to remove residual solvent. Then drying and oiling at 160 ℃, treating for 3min at 380 ℃ in a nitrogen environment, and winding to obtain the finished fiber, wherein the fiber properties are shown in table 2.
As can be seen from the data in Table 2, the comparative examples have higher dry yarn strength in the case of m-phenylenediamine (MPDA), 4 '-diaminodiphenyl ether (DADPE) or 3,4' -diaminodiphenyl ether (MADPE) without introducing the repeating unit (III) and chlorine-containing p-phenylenediamine (Cl-PPDA) or 2, 5-diaminobenzonitrile (CN-PPDA) modifying monomer of the repeating unit (IV), but have much lower tensile ratios than those of inventive examples 6 to 14, and inventive examples 6 to 14 can maintain higher strength and significantly improve the dipping filament strength while greatly increasing the fiber elongation by introducing the modifying monomers. Meanwhile, as can also be seen from fig. 1, the elongation of the fibers of examples 2, 9, 11 of the present invention is much higher than that of the prior art (comparative example), and the strength is comparable to that of the comparative example. Therefore, the high-strength high-elongation heterocyclic aromatic polyamide fiber has wide application prospects in the fields of national defense and military industry, particularly the bulletproof field and the special rubber reinforcement field.
Claims (10)
1. A high-strength high-elongation heterocyclic aromatic polyamide fiber characterized by: the molecular composition structure of the heterocyclic aromatic polyamide is formed by randomly connecting 4 kinds of repeating units with the following structural formula,
wherein the content of the first and second substances,
ar in the repeating unit (III) 1 Is composed of
At least one of;
ar in the repeating unit (IV) 2 Is composed of
At least one of (a);
the mol percentage content of each repeating unit in the molecular composition structure is as follows:
the content of the repeating unit (I) is 40-90%;
the content of the repeating unit (II) is 0 to 30 percent;
the content of the repeating unit (III) is 5 to 30 percent;
the content of the repeating unit (IV) is 5 to 30 percent;
the high-strength and high-elongation heterocyclic aromatic polyamide fiber has tensile breaking strength of 28.0-35.0 cN/dtex and elongation of 4.5-10.0%.
2. The process for preparing high-strength high-elongation heterocyclic aromatic polyamide fiber according to claim 1, characterized in that: the method comprises the following steps:
A. preparation of polymerization stock solution: dissolving diamine monomers in proportion into an organic solvent containing solubilizing salts, then adding terephthaloyl chloride, and stirring and reacting under the protection of nitrogen to obtain a polymer solution;
the solid content of the polymer solution is 3-10%, and the dynamic viscosity is 3-80 ten thousand centipoise at room temperature;
B. spinning: transferring the polymer solution obtained in the step A into a defoaming kettle, defoaming, filtering, extruding the polymer solution through a spinneret orifice, coagulating and forming the polymer solution in a coagulating bath to obtain nascent fibers, plastically stretching, washing, drying and oiling the nascent fibers, then performing a heat treatment process, and finally winding to obtain finished fibers.
3. The process for preparing high-strength high-elongation heterocyclic aromatic polyamide fiber according to claim 2, characterized in that: in the step A, the dissolution-assisting salt is LiCl or CaCl 2 The solid content of the solubilizing salt in the organic solvent is 2.0-7.5%.
4. The process for preparing high-strength high-elongation heterocyclic aromatic polyamide fiber according to claim 2 or 3, characterized in that: in the step A, the organic solvent is one of N, N-dimethylacetamide and N-methylpyrrolidone.
5. The process for preparing high-strength high-elongation heterocyclic aromatic polyamide fiber according to claim 2, characterized in that: in the step A, the coagulating bath uses an aqueous solution of N, N-dimethylacetamide or N-methylpyrrolidone with the mass fraction of 30-65%.
6. The process for preparing a high-strength high-elongation heterocyclic aromatic polyamide fiber according to claim 2 or 3, characterized in that: in the step A, the temperature of the coagulating bath is 0-40 ℃.
7. The process for preparing high-strength high-elongation heterocyclic aromatic polyamide fiber according to claim 2, characterized in that: in the step B, the plastic stretching is carried out in an aqueous solution of N, N-dimethylacetamide or N-methylpyrrolidone with the mass fraction of 10-25% at the temperature of 20-70 ℃.
8. The process for preparing high-strength high-elongation heterocyclic aromatic polyamide fiber according to claim 2, characterized in that: in the step B, the water used in the water washing procedure is hot water with the temperature of 80-95 ℃.
9. The process for preparing high-strength high-elongation heterocyclic aromatic polyamide fiber according to claim 2, characterized in that: in the step B, the drying temperature of the drying procedure is 120-200 ℃.
10. The process for preparing high-strength high-elongation heterocyclic aromatic polyamide fiber according to claim 2, characterized in that: in the step B, the heat treatment process is to carry out heat treatment for 0.5 to 5min at 320 to 450 ℃ in the air or nitrogen environment.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5643518A (en) * | 1995-03-29 | 1997-07-01 | Industrial Technology Research Institute | Process for preparing fibers of soluble wholly aromatic polyamides |
| CN101501254A (en) * | 2006-07-26 | 2009-08-05 | 帝人高科技产品株式会社 | Aromatic polyamide fiber and process for producing the same and protective clothing using said aromatic polyamide fiber |
| JP2012207325A (en) * | 2011-03-29 | 2012-10-25 | Teijin Techno Products Ltd | Para-type wholly aromatic polyamide fiber |
| CN104233499A (en) * | 2013-06-17 | 2014-12-24 | 东华大学 | Preparation method of aromatic polyarmide fiber containing heterlcyclic rings |
| JP2016196599A (en) * | 2015-04-06 | 2016-11-24 | 帝人株式会社 | Wholly aromatic polyamide fiber |
| CN107675283A (en) * | 2017-08-15 | 2018-02-09 | 崔松 | High-strength aromatic coplyamide fibre and preparation method thereof |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5643518A (en) * | 1995-03-29 | 1997-07-01 | Industrial Technology Research Institute | Process for preparing fibers of soluble wholly aromatic polyamides |
| CN101501254A (en) * | 2006-07-26 | 2009-08-05 | 帝人高科技产品株式会社 | Aromatic polyamide fiber and process for producing the same and protective clothing using said aromatic polyamide fiber |
| JP2012207325A (en) * | 2011-03-29 | 2012-10-25 | Teijin Techno Products Ltd | Para-type wholly aromatic polyamide fiber |
| CN104233499A (en) * | 2013-06-17 | 2014-12-24 | 东华大学 | Preparation method of aromatic polyarmide fiber containing heterlcyclic rings |
| JP2016196599A (en) * | 2015-04-06 | 2016-11-24 | 帝人株式会社 | Wholly aromatic polyamide fiber |
| CN107675283A (en) * | 2017-08-15 | 2018-02-09 | 崔松 | High-strength aromatic coplyamide fibre and preparation method thereof |
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